Catalyst Composition with Phosphorus-Based Donor and Method

ABSTRACT

Disclosed are catalyst compositions having an external electron donor which includes one or more of the following compositions: a phosphite, a phosphonite, a pyrophosphite, and/or a diphosphazane. Ziegler-Natta catalyst compositions containing the present external electron donor exhibit strong activity and produce propylene-based olefins with high isotacticity and high melt flow rate.

CROSS REFERENCE TO RELATED APPLICATION

This application claims priority to U.S. provisional application Ser.No. 61/141,170 filed on Dec. 26, 2008, the entire content of which isincorporated by reference herein

BACKGROUND

The present disclosure relates to catalyst compositions with an externalelectron donor comprising one or more of the following: a phosphite, aphosphonite, a pyrophosphite (diphosphite), and/or a diphosphazane(iminodiphosphite), and the resultant olefin-based polymers producedtherefrom.

Known are Ziegler-Natta catalyst compositions for the production ofolefin-based polymers. Ziegler-Natta catalyst compositions typicallyinclude a procatalyst containing a transition metal halide (i.e.,titanium, chromium, vanadium), a cocatalyst such as an organoaluminumcompound, and optionally an external electron donor and/or an activitylimiting agent. The art presently recognizes a finite set of compoundssuitable for use as external electron donors. With the continueddiversification and sophistication of applications for olefin-basedpolymers, the art recognizes the need for olefin-based polymers withimproved and varied properties. Desirable would be external electrondonors for Ziegler-Natta catalyst compositions that contribute to strongcatalyst activity and high hydrogen response during polymerization.Further desired are external electron donors for Ziegler-Natta catalyststhat produce propylene-based polymers with high isotacticity, high meltflow rate, and low toxicity.

SUMMARY

The present disclosure is directed to catalyst compositions with anexternal electron donor which includes one or more of the following: aphosphite, a phosphonite, a pyrophosphite, and/or a diphosphazane. Theexternal electron donors of the present disclosure exhibit highcompatibility with Ziegler-Nata procatalyst compositions and contributeto high catalyst activity and high hydrogen response when combined withthese procatalysts. In addition, the present external electron donorsproduce olefin-based polymers with high isotacticity and high melt flowrate when used in conjunction with Ziegler-Natta procatalystcompositions.

In an embodiment, a catalyst composition is provided. The catalystcomposition includes a procatalyst composition, cocatalyst, and anexternal electron donor. The procatalyst composition includes amagnesium moiety. The external electron donor includes a phosphite andoptionally an alkoxysilane. The catalyst composition may optionallyinclude an activity limiting agent.

In an embodiment, the procatalyst composition includes a combination ofthe magnesium moiety, a titanium moiety, and/or an internal electrondonor.

In an embodiment, the internal electron donor of the procatalystcomposition may be an aromatic acid ester, a diether, a silyl ester andcombinations thereof.

In an embodiment, the external electron donor includes a phosphite ofthe structure (VI) as provided below.

R₁, R₂, and R₃ of structure (VI) are the same or different. Each ofR₁-R₃ is selected from a substituted hydrocarbyl group having 1 to 20carbon atoms, an unsubstituted hydrocarbyl group having 1 to 20 carbonatoms, and combinations thereof. In another embodiment, R₁-R₃ are thesame or different, and each of R₁-R₃ is selected from a C₁-C₆ alkylgroup. In a further embodiment, at least two R groups of R₁-R₃ aremembers of a P-ring structure.

Another catalyst composition is provided in the present disclosure. Inan embodiment, a catalyst composition is provided which includes aprocatalyst composition, cocatalyst, and an external electron donor. Theprocatalyst composition includes a magnesium moiety. The externalelectron donor includes a phosphonite (or related compound) andoptionally an alkoxysilane. The catalyst composition may optionallyinclude an activity limiting agent.

In an embodiment, the external electron donor includes a phosphonite ofthe structure (IX) as provided below.

R₁ and R₂ are the same or different. Each of R₁ and R₂ is selected froma hydrocarbyl group having 1 to 20 carbon atoms, a substitutedhydrocarbyl group having 1 to 20 carbon atoms, and combinations thereof.X is selected from a hydrocarbyl group having 1 to 20 carbon atoms, asubstituted hydrocarbyl group having 1 to 20 carbon atoms, a substitutedamino group, an unsubstituted amino group a halide, a pseudohalide, anda hydroxyl group.

In an embodiment, any of R₁, R₂ and/or X is a member of a P-ringstructure.

Another catalyst composition is provided in the present disclosure. Inan embodiment, a catalyst composition is provided which includes aprocatalyst composition, cocatalyst, and an external electron donor. Theprocatalyst composition includes a magnesium moiety. The externalelectron donor includes a pyrophosphite and optionally an alkoxysilane.The catalyst composition may optionally include an activity limitingagent.

In an embodiment, the external electron donor includes a pyrophosphiteof the structure (XI) as provided below.

R₁, R₂, R₃ and R₄ are the same or different. Each of R₁-R₄ is selectedfrom a substituted hydrocarbyl group having 1 to 20 carbon atoms, anunsubstituted hydrocarbyl group having 1 to 20 carbon atoms, andcombinations thereof. In an embodiment, any R group of R₁-R₄ may be amember of a P-ring structure.

Another catalyst composition is provided in the present disclosure. Inan embodiment, a catalyst composition is provided which includes aprocatalyst composition, cocatalyst, and an external electron donor. Theexternal electron donor includes a diphosphazane and optionally analkoxysilane. The catalyst composition may optionally include anactivity limiting agent.

In an embodiment, the external electron donor includes a diphosphazaneof the structure (XII) as provided below.

R₁, R₂, R₃ R₄ and R₅ are the same or different. Each of R₁-R₅ isselected from a substituted hydrocarbyl group having 1 to 20 carbonatoms, an unsubstituted hydrocarbyl group having 1 to 20 carbon atoms,and combinations thereof. In an embodiment, at least one R group ofR₁-R₅ may be a member of a P-ring structure.

A polymerization process is provided in the present disclosure. In anembodiment, the polymerization process includes contacting, underpolymerization conditions, an olefin with a catalyst composition. Thecatalyst composition may be any of the foregoing catalyst compositions.The catalyst composition contains an external electron donor comprisingone or more of the following: a phosphite, a phosphonite, apyrophosphite, a diphosphazane, and any combination thereof. Thecatalyst composition may optionally include an alkoxysilane and/or anactivity limiting agent. The process includes forming an olefin-basedpolymer.

In an embodiment, the olefin is propylene. The process includes forminga propylene-based polymer having a melt flow rate from about 0.01 g/10min to about 2000 g/10 min.

In an embodiment, the olefin is propylene. The process includes forminga propylene-based polymer having a xylene solubles content from about0.5% to about 10%.

An advantage of the present disclosure is the provision of an improvedexternal electron donor.

An advantage of the present disclosure is the provision of an improvedcatalyst composition for the polymerization of olefin-based polymers.

An advantage of the present disclosure is the provision of an improvedZiegler-Natta catalyst composition.

An advantage of the present disclosure is a catalyst composition with anexternal electron donor that contains a phosphite, and/or a phosphonite,and/or a pyrophosphite, and/or a diphosphazane, the catalyst compositionexhibiting improved activity and/or improved hydrogen response duringpolymerization.

An advantage of the present disclosure is a catalyst composition with anexternal electron donor that contains a phosphite, and/or a phosphonite,and/or a pyrophosphite, and/or a diphosphazane, the catalyst compositionproducing olefin-based polymers with high isotacticity and/or high meltflow rate.

DETAILED DESCRIPTION

In an embodiment, a catalyst composition is provided. As used herein, “acatalyst composition” is a composition that forms an olefin-basedpolymer when contacted with an olefin under polymerization conditions.The catalyst composition includes a procatalyst composition, acocatalyst, and an external electron donor. The external electron donorcomprises a phosphite. The catalyst composition may optionally includean activity limiting agent.

The procatalyst composition may include (i) magnesium; (ii) a transitionmetal compound of an element from Periodic Table groups IV to VIII;(iii) a halide, an oxyhalide, and/or an alkoxide of (i) and/or (ii);(iv) an internal electron donor; and (v) combinations of (i), (ii),(iii), and (iv). Nonlimiting examples of suitable procatalyst componentsinclude halides, oxyhalides, and alkoxides of magnesium, titanium,vanadium, chromium, molybdenum, zirconium, hafnium, and combinationsthereof.

In an embodiment, the procatalyst composition includes a magnesiummoiety. Nonlimiting examples of suitable magnesium moieties includeanhydrous magnesium chloride and/or its alcohol adduct, magnesiumalkoxide or aryloxide, mixed magnesium alkoxy halide, and/orcarboxylated magnesium dialkoxide or aryloxide. In another embodiment,the magnesium moiety is a magnesium di-(C₁₋₄)alkoxide, such asdiethoxymagnesium. In another embodiment, the magnesium moiety ismagnesium chloride.

In an embodiment, the procatalyst composition includes a titaniummoiety. Nonlimiting examples of suitable titanium moieties includetitanium alkoxides, titanium aryloxides, titanium alkoxy halides, andtitanium halides. In a further embodiment, the titanium moiety istitanium tetrachloride.

The procatalyst composition also includes an internal electron donor. Asused herein, an “internal electron donor” is a compound added duringformation of the procatalyst composition that donates a pair ofelectrons to one or more metals present in the resultant procatalystcomposition. Not bounded by any particular theory, it is believed thatthe internal electron donor assists in regulating the formation ofactive sites thereby enhancing catalyst stereoselectivity.

In an embodiment, the procatalyst composition is produced by way ofhalogenation which converts a procatalyst precursor and the internalelectron donor into a combination or a complex of a magnesium moiety anda titanium moiety into which the internal electron donor isincorporated. The magnesium moiety and the titanium moiety may be anyrespective magnesium or titanium moiety as disclosed herein.

In an embodiment, the internal electron donor is an aromatic acid ester,a diether, a silyl ester, and combinations thereof.

In an embodiment, the internal electron donor is an aromatic acid ester.As used herein, an “aromatic acid ester” is a monocarboxylic acid esteror a polycarboxylic acid ester that includes structure (I) as follows:

wherein R₁ is selected from a hydrocarbyl having 1 to 10 carbon atoms, asubstituted hydrocarbyl having 1 to 10 carbon atoms, a alkoxycarbonylgroup, and a heteroatom or heteroatom-containing group. As used herein,the term “hydrocarbyl” and “hydrocarbon” refer to substituentscontaining only hydrogen and carbon atoms, including branched orunbranched, saturated or unsaturated, cyclic, polycyclic or acyclicspecies, and combinations thereof. Nonlimiting examples of hydrocarbylgroups include alkyl-, cycloalkyl-, alkenyl-, alkadienyl-,cycloalkenyl-, cycloalkadienyl-, aryl-, aralkyl, alkylaryl, and alkynyl-groups.

As used herein, the terms “substituted hydrocarbyl” and “substitutedhydrocarbon” refer to a hydrocarbyl group that is substituted with oneor more nonhydrocarbyl substituent groups. A nonlimiting example of anonhydrocarbyl substituent group is a heteroatom. As used herein, a“heteroatom” refers to an atom other than carbon or hydrogen. Theheteroatom can be a non-carbon atom from Groups IV, V, VI, and VII ofthe Periodic Table. Nonlimiting examples of heteroatoms include: F, Cl,Br, N, O, P, B, S, and Si. As used herein, the term “halohydrocarbyl”refers to a hydrocarbyl that is substituted with one or more halogenatoms.

In an embodiment, the hydrocarbyl group of R₁ of structure (I) caninclude a substituted- or unsubstituted-hydrocarbyl group having 1 to 10carbon atoms.

R₂-R₆ of the aromatic acid ester of structure (I) are the same ordifferent, each being selected from hydrogen, a hydrocarbyl group having1 to 10 carbon atoms, a substituted hydrocarbyl group having 1 to 10atoms, a carboxylate having 1 to 10 carbon atoms, a heteroatom, andcombinations thereof.

In an embodiment, the aromatic acid ester is a benzoic acid ester. Asused herein, “benzoic acid ester” is a monocarboxylic acid ester withthe structure (II) below:

wherein R₁ is the same as R₁ of structure (I). A₂-A₆ are the same ordifferent and each is selected from hydrogen, a hydrocarbyl group having1 to 10 carbon atoms, a substituted hydrocarbyl group having 1 to 10atoms, a heteroatom, and combinations thereof. Nonlimiting examples ofsuitable benzoic acid esters include an alkyl p-alkoxybenzoate (such asethyl p-methoxybenzoate, methyl p-ethoxybenzoate, ethylp-ethoxybenzoate), an alkyl benzoate (such as ethyl benzoate, methylbenzoate), an alkyl p-halobenzoate (ethyl p-chlorobenzoate, ethylp-bromobenzoate), a benzoyl halide (such as benzoyl chloride), andbenzoic anhydride. In an embodiment, the benzoic acid ester is selectedfrom ethyl benzoate, benzoyl chloride, ethyl p-bromobenzoate, n-propylbenzoate, and benzoic anhydride. In another embodiment, the benzoic acidester is ethyl benzoate.

In an embodiment, the aromatic acid ester is a phthalic acid ester. Asused herein, a “phthalic acid ester” refers to a polycarboxylic acidester with the structure (III) below.

wherein R₁ and R₂ are the same or different and each is selected from ahydrocarbyl having 1 to 10 carbon atoms and a substituted hydrocarbylgroup having 1 to 10 carbon atoms. B₁-B₄ are the same or different andeach is selected from hydrogen, a hydrocarbyl group having 1 to 10carbon atoms, a substituted hydrocarbyl group having 1 to 10 atoms, aheteroatom, and combinations thereof. Nonlimiting examples of suitablephthalic acid esters include dimethyl phthalate, diethyl phthalate,di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate,diisobutyl phthalate, di-tert-butyl phthalate, diisoamyl phthalate,di-tert-amyl phthalate, dineopentyl phthalate, di-2-ethylhexylphthalate, di-2-ethyldecyl phthalate, bis(2,2,2-trifluoroethyl)phthalate, diisobutyl 4-t-butylphthalate, and diisobutyl4-chlorophthalate. In an embodiment, the phthalic acid ester isdiisobutyl phthalate.

In an embodiment, the aromatic acid ester includes acyl halides oranhydrides. Not wishing to be bound by any particular theory, it isbelieved that the acyl halides and/or anhydrides react with the ethoxidespecies in the procatalyst precursor to form the corresponding ethylesters. In an embodiment, benzoyl chloride is used alone or incombination with ethyl benzoate. In another embodiment, phthaloylchloride and/or phthalic anhydride is used to replace phthalate.

In an embodiment, the internal electron donor is a di-ether. Thedi-ether may be a dialkyl di-ether compound represented by the structure(IV).

wherein R₁ to R₄ are independently of one another an alkyl, aryl oraralkyl group having up to 20 carbon atoms, which may optionally containa group 14, 15, 16, or 17 heteroatom, provided that R₁ and R₂ may be ahydrogen atom. The dialkylether may be linear or branched, and mayinclude one or more of the following groups: alkyl, cycloaliphatic,aryl, alkylaryl or arylalkyl radicals with 1-18 carbon atoms, andhydrogen. Nonlimiting examples of suitable dialkyl diether compoundsinclude dimethyl diether, diethyl diether, dibutyl diether, methyl ethyldiether, methyl butyl diether, methyl cyclohexyl diether,2,2-dimethyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane,2,2-di-n-butyl-1,3-dimethoxypropane,2,2-diiso-butyl-1,3-dimethoxypropane,2-ethyl-2-n-butyl-1,3-dimethoxypropane,2-n-propyl-2-cyclopentyl-1,3-dimethoxypropane,2,2-dimethyl-1,3-diethoxypropane,2-n-propyl-2-cyclohexyl-1,3-diethoxypropane,2-(2-ethylhexyl)-1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane,2-n-butyl-1,3-dimethoxypropane, 2-sec-butyl-1,3-dimethoxypropane,2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-diethoxypropane,2-cumyl-1,3-diethoxypropane, 2-(2-phenylethyl)-1,3-dimethoxypropane,2-(2-cyclohexylethyl)-1,3-dimethoxypropane,2-(p-chlorophenyl)-1,3-dimethoxypropane,2-(diphenylmethyl)-1,3-dimethoxypropane,2-(1-naphthyl)-1,3-dimethoxypropane,2-(fluorophenyl)-1,3-dimethoxypropane,2-(1-decahydronaphthyl)-1,3-dimethoxypropane,2-(p-t-butylphenyl)-1,3-dimethoxypropane,2,2-dicyclohexyl-1,3-dimethoxypropane,2,2-di-n-propyl-1,3-dimethoxypropane,2-methyl-2-n-propyl-1,3-dimethoxypropane,2-methyl-2-benzyl-1,3-dimethoxypropane,2-methyl-2-ethyl-1,3-dimethoxypropane,2-methyl-2-phenyl-1,3-dimethoxypropane,2-methyl-2-cyclohexyl-1,3-dimethoxypropane,2,2-bis(p-chlorophenyl)-1,3-dimethoxypropane,2,2-bis(2-cyclohexylethyl)-1,3-dimethoxypropane,2-methyl-2-isobutyl-1,3-dimethoxypropane,2-methyl-2-(2-ethylhexyl)-1,3-dimethoxy propane,2-methyl-2-isopropyl-1,3-dimethoxypropane,2,2-diphenyl-1,3-dimethoxypropane, 2,2-dibenzyl-1,3-dimethoxypropane,2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane,2,2-diisobutyl-1,3-diethoxypropane,2,2-diisobutyl-1,3-di-n-butoxypropane,2-isobutyl-2-isopropyl-1,3-dimethoxypropane,2,2-di-sec-butyl-1,3-dimethoxypropane,2,2-di-t-butyl-1,3-dimethoxypropane,2,2-dineopentyl-1,3-dimethoxypropane,2-isopropyl-2-isopentyl-1,3-dimethoxypropane,2-phenyl-2-benzyl-1,3-dimethoxypropane,2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane,2-isopropyl-2-(3,7-dimethyloctyl)1,3-dimethoxypropane,2,2-diisopropyl-1,3-dimethoxypropane,2-isopropyl-2-cyclohexylmethyl-1,3-dimethoxypropane,2,2-diisopentyl-1,3-dimethoxypropane,2-isopropyl-2-cyclohexyl-1,3-dimethoxypropane,2-isopropyl-2-cyclopentyl-1,3-dimethoxypropane,2,2-dicyclopentyl-1,3-dimethoxypropane,2-n-heptyl-2-n-pentyl-1,3-dimethoxypropane,9,9-bis(methoxymethyl)fluorene,1,3-dicyclohexyl-2,2-bis(methoxymethyl)propane,3,3-bis(methoxymethyl)-2,5-dimethylhexane, or any combination of theforegoing. In an embodiment, the internal electron donor is1,3-dicyclohexyl-2,2-bis(methoxymethyl)propane,3,3-bis(methoxymethyl)-2,5-dimethylhexane,2,2-dicyclopentyl-1,3-dimethoxypropane and combinations thereof.

In an embodiment, the internal electron donor may include a silyl ester.In one embodiment, the silyl ester can be any silyl ester as disclosedin co-pending U.S. Patent Application Ser. No. 61/117,820 (AttorneyDocket No. 67098) filed on Nov. 25, 2008, the entire content of which isincorporated by reference herein.

In an embodiment, the silyl ester has the structure (V) as shown below.

The letters “m” and “n” are each an integer from 1 to 5, m and n beingthe same or different, m and n each denoting the number of carbon atomsin the respective carbon chain. It is understood that each additionalcarbon in the C_(m) carbon chain and/or the C_(n) carbon chain caninclude one or more R′ substituent(s). The R′ substituent(s) can behydrogen or a substituted/unsubstituted hydrocarbyl group having 1 to 20carbon atoms.

The substituents R₁, R₂, R₃, R₄, R₅, R₆ and R₇ of structure (V) can bethe same or different. Each of R₁-R₇ is selected from hydrogen, asubstituted hydrocarbyl group having 1 to 20 carbon atoms, anunsubstituted hydrocarbyl group having 1 to 20 carbon atoms, andcombinations thereof.

The symbol “X” of structure (V) represents an electron donating group.The term “electron donating group” refers to a functional group thatdonates one or more electron pairs to the procatalyst precursor. Theelectron pair is typically donated during procatalyst formation, such asduring halogenation, for example. Nonlimiting examples of suitableelectron donating groups include —C(═O)OR, —O(O═)CR, —(O═)CNHR,—(O═)CNRR′, —NH(O═)CR, —NR′(O═)CR, —C(═O)R, —OR, —NHR, —NR′R, —SR,S(═O)R, —S(═O)₂R, —OS(═O)₂(OR), and combinations thereof. R and R′ ofelectron donating group X can be a substituted or an unsubstitutedhydrocarbyl group having 1 to 20 carbon atoms.

In an embodiment, the internal electron donor may be a mixed internalelectron donor as disclosed in co-pending U.S. Patent Application Ser.No. 61/117,763 (Attorney Docket No. 67097) filed on Nov. 25, 2008, theentire content of which is incorporated by reference herein.

In an embodiment, the procatalyst composition includes a combination ofa magnesium moiety, a titanium moiety, and one or more internal electrondonors. The magnesium moiety, the titanium moiety, and the internalelectron donor(s) may be any respective composition as disclosed herein.

In an embodiment, the procatalyst composition is a mixedmagnesium/titanium compound (“MagTi”) complexed with the internalelectron donor. The “MagTi compound” has the formulaMg_(d)Ti(OR^(e))_(f)X_(g)(IED) wherein R^(e) is an aliphatic or aromatichydrocarbon radical having 1 to 14 carbon atoms or COR′ wherein R′ is analiphatic or aromatic hydrocarbon radical having 1 to 14 carbon atoms;each OR^(e) group is the same or different; X is independently chlorine,bromine or iodine, preferably chlorine; d is 0.5 to 56, or 2 to 4; f is2 to 116 or 5-15; and g is 0.5 to 116, or 1 to 3. The term “IED” refersto the internal electron donor. The internal electron donor may be anyinternal electron donor disclosed herein. Nonlimiting examples of MagTicompounds include procatalysts under the trade name SHAC, available fromThe Dow Chemical Company, Midland, Mich.

In an embodiment, the procatalyst composition has a titanium content offrom about 0.1 percent by weight to about 6.0 percent by weight, basedon the total solids weight, or from about 1.0 percent by weight to about4.5 percent by weight, or from about 1.5 percent by weight to about 3.5percent by weight. The weight ratio of titanium to magnesium in thesolid procatalyst composition is suitably between about 1:3 and about1:160, or between about 1:4 and about 1:50, or between about 1:6 and1:30. Weight percent is based on the total weight of the procatalystcomposition.

In an embodiment, the magnesium to internal electron donor molar ratiois from about 100:1 to about 1:1, or from about 30:1 to about 2:1, orfrom about 15:1 to about 3:1. Weight percent is based on the totalweight of the procatalyst composition.

In another embodiment, the procatalyst composition includes a magnesiumchloride support upon which a titanium chloride is deposited and intowhich the internal electron donor is incorporated.

Ethoxide content in the procatalyst composition indicates thecompleteness of conversion of precursor metal ethoxide into a metalhalide. The internal electron donor assists in converting ethoxide intohalide during halogenation. In an embodiment, the procatalystcomposition includes from about 0.01 wt % to about 1.0 wt %, or fromabout 0.05 wt % to about 0.5 wt % ethoxide. Weight percent is based onthe total weight of the procatalyst composition.

In an embodiment, the internal electron donor is free of phosphorousatom(s) or is otherwise void of phosphorus atom(s). In anotherembodiment, the procatalyst composition is free of phosphorus atom(s) oris otherwise void of phosphorus atoms.

The present catalyst composition includes a cocatalyst. As used herein,a “cocatalyst” is a substance capable of converting the procatalyst toan active polymerization catalyst. The cocatalyst may include hydrides,alkyls, or aryls of aluminum, lithium, zinc, tin, cadmium, beryllium,magnesium, and combinations thereof. In an embodiment, the cocatalyst isa hydrocarbyl aluminum cocatalyst represented by the formula R₃Alwherein each R is an alkyl, cycloalkyl, aryl, or hydride radical; atleast one R is a hydrocarbyl radical; two or three R radicals can bejoined in a cyclic radical forming a heterocyclic structure; each R canbe the same or different; and each R, which is a hydrocarbyl radical,has 1 to 20 carbon atoms, and preferably 1 to 10 carbon atoms. In afurther embodiment, each alkyl radical can be straight or branched chainand such hydrocarbyl radical can be a mixed radical, i.e., the radicalcan contain alkyl, aryl, and/or cycloalkyl groups. Nonlimiting examplesof suitable radicals are: methyl, ethyl, propyl, isopropyl, butyl,isobutyl, tert-butyl, pentyl, neopentyl, hexyl, 2-methylpentyl, heptyl,octyl, isooctyl, 2-ethylhexyl, 5,5-dimethylhexyl, nonyl, decyl,isodecyl, undecyl, dodecyl, phenyl, phenethyl, methoxyphenyl, benzyl,tolyl, xylyl, naphthyl, naphthal, methylnapthyl, cyclohexyl,cycloheptyl, and cyclooctyl.

Nonlimiting examples of suitable hydrocarbyl aluminum compounds are asfollows: triisobutylaluminum, trihexylaluminum, di-isobutylaluminumhydride, dihexylaluminum hydride, isobutylaluminum dihydride,hexylaluminum dihydride, di-isobutylhexylaluminum, isobutyldihexylaluminum, trimethylaluminum, triethylaluminum, tripropylaluminum,triisopropylaluminum, tri-n-butylaluminum, trioctylaluminum,tridecylaluminum, tridodecylaluminum, tribenzylaluminum,triphenylaluminum, trinaphthylaluminum, and tritolylaluminum. In anembodiment, the cocatalyst is selected from triethylaluminum,triisobutylaluminum, trihexylaluminum, di-isobutylaluminum hydride, anddihexylaluminum hydride.

In an embodiment, the cocatalyst is a hydrocarbyl aluminum compoundrepresented by the formula R_(n)AlX_(3-n) wherein n=1 or 2, R is analkyl, and X is a halide or alkoxide. Nonlimiting examples of suitablecompounds are as follows: methylaluminoxane, isobutylaluminoxane,diethylaluminum ethoxide, diisobutylaluminum chloride,tetraethyldialuminoxane, tetraisobutyldialuminoxane, diethylaluminumchloride, ethylaluminum dichloride, methylaluminum dichloride, anddimethylaluminum chloride.

In an embodiment, the cocatalyst is triethylaluminum. The molar ratio ofaluminum to titanium is from about 5:1 to about 500:1, or from about10:1 to about 200:1, or from about 15:1 to about 150:1, or from about20:1 to about 100:1. In another embodiment, the molar ratio of aluminumto titanium is about 45:1.

The present catalyst composition includes an external electron donor. Asused herein, an “external electron donor” is a compound addedindependent of procatalyst formation and contains at least onefunctional group that is capable of donating a pair of electrons to ametal atom. In an embodiment, the external electron donor includes aphosphorus-based compound. As used herein, a “phosphorus-based” compoundis a compound which includes one or more phosphorus atom(s) and excludescompounds with a phosphoryl group (P═O), with exception to tautomersdisclosed herein. In an embodiment, the phosphorus-based compoundincludes one or more of the following: a phosphite, a phosphonite, apyrophosphite, a phosphazane, and a diphosphazane. Bounded by noparticular theory, it is believed that the present phosphorus-basedexternal electron donor enhances hydrogen response and/or catalyststereoselectivity, (i.e., increases polymer melt flow at a givenhydrogen/monomer ratio and/or reduces xylene soluble material in theformant polymer).

In an embodiment, the external electron donor includes a phosphite. Thephosphite has the structure (VI):

wherein R₁, R₂, and R₃ are the same or different. Each of R₁-R₃ isselected from a substituted hydrocarbyl group having 1 to 20 carbonatoms, an unsubstituted hydrocarbyl group having 1 to 20 carbon atoms,and combinations thereof.

In an embodiment, R₁-R₃ of structure (VI) are the same or different, andeach of R₁-R₃ is selected from a C₁-C₆ alkyl group, and combinationsthereof.

In an embodiment, R₁-R₃ of structure (VI) are the same or different andeach of R₁-R₃ is selected from a methyl group, an ethyl group, a propylgroup, an isopropyl group, a butyl group, an isobutyl group, a C₅ ringstructure, a C₆ ring structure, and combinations thereof. As usedherein, a “C₅ ring structure” is a cyclic structure containing fivecarbon atoms. A “C₆ ring structure” is a cyclic structure containing sixcarbon atoms. A ring structure may be aromatic or may be non-aromatic. Aring structure may be mono-cyclic or poly-cyclic and may be ahydrocarbyl or may include a heteroatom. A nonlimiting example of a C₅ring structure is a cyclopentyl group. Nonlimiting examples of a C₆ ringstructure include a cyclohexyl group or a phenyl group. A nonlimitingexample of a polycyclic ring structure is a fluorene-based compound.

In an embodiment, each of R₁-R₂ of structure (VI) is a methyl group andR₃ is selected from a methyl group, an ethyl group, a propyl group, anisopropyl group, a butyl group, an isobutyl group, a C₅ ring structure,and a C₆ ring structure.

In an embodiment, each of R₁-R₂ of structure (VI) is an ethyl group andR₃ is selected from a methyl group, an ethyl group, a propyl group, anisopropyl group, a butyl group, an isobutyl group, a C₅ ring structure,a C₆ ring structure, and a poly-cyclic ring structure that is afluorene-based compound.

In an embodiment, each of R₁-R₂ of structure (VI) is an ethyl group andR₃ of structure (VI) is a methyl group.

In an embodiment, each of R₁-R₂ of structure (VI) is an ethyl group andR₃ is a propyl group.

In an embodiment, each of R₁-R₃ of structure (VI) is an butyl group.

In an embodiment, each of R₁-R₃ of structure (VI) is an ethyl group.

In an embodiment, at least one, or at least two R groups of R₁-R₃ aremembers of a P-ring structure. As used herein, a “P-ring structure” is aring structure which includes at least one P—O linkage. The P-ringstructure may be a monocyclic structure or a polycyclic structure. TheP-ring structure may or may not be aromatic. Nonlimiting examples ofsuitable members for the P-ring structure include the following atoms:C, O, P, N, and S. In an embodiment, the P-ring structure includes from5 to 8 members. In an further embodiment, each of R₁-R₃ are members of aP-ring structure.

Nonlimiting examples of suitable P-ring structures for structure (VI)are set forth in Table A below.

TABLE A Structure Name

2-ethoxy-1,3,2-dioxaphospholane

2-ethoxy-1,3,2-dioxaphosphinane

2-ethoxy-1,3,2-dioxaphosphepane

In an embodiment, the external electron donor may be complexed in wholeor in part with the cocatalyst.

In an embodiment, the external electron donor includes a phosphite andone or more alkoxysilanes. The phosphite can be any phosphite asdisclosed herein. The alkoxysilane has the general formula:SiR_(m)(OR′)_(4-m) (I) where R independently each occurrence is hydrogenor a hydrocarbyl or an amino group optionally substituted with one ormore substituents containing one or more Group 14, 15, 16, or 17heteroatoms, said R containing up to 20 atoms not counting hydrogen andhalogen; R′ is a C₁₋₂₀ alkyl group; and m is 0, 1, 2 or 3. In anembodiment, R is C₆₋₁₂ aryl, alkyl or aralkyl, C₃₋₁₂ cycloalkyl, C₃₋₁₂branched alkyl, or C₃₋₁₂ cyclic or acyclic amino group, R′ is C₁₋₄alkyl, and m is 1 or 2. Nonlimiting examples of suitable silanecompositions include dicyclopentyldimethoxysilane,di-tert-butyldimethoxysilane, methylcyclohexyldimethoxysilane,methylcyclohexyldiethoxysilane, ethylcyclohexyldimethoxysilane,diphenyldimethoxysilane, diisopropyldimethoxysilane,di-n-propyldimethoxysilane, diisobutyldimethoxysilane,diisobutyldiethoxysilane, di-n-butyldimethoxysilane,cyclopentyltrimethoxysilane, isopropyltrimethoxysilane,n-propyltrimethoxysilane, n-propyltriethoxysilane, ethyltriethoxysilane,tetramethoxysilane, tetraethoxysilane, diethylaminotriethoxysilane,cyclopentylpyrrolidinodimethoxysilane, bis(pyrrolidino)dimethoxysilane,bis(perhydroisoquinolino)dimethoxysilane, and dimethyldimethoxysilane.In an embodiment, the alkoxysilane is dicyclopentyldimethoxysilane,methylcyclohexyldimethoxysilane, n-propyltrimethoxysilane, and anycombination of thereof. In another embodiment, the alkoxysilane isdicyclopentyldimethoxysilane.

In an embodiment, the external electron donor may include from about 0.1mol % to about 99.9% mol % phosphite and from about 99.9 mol % to about0.1 mol % alkoxysilane.

In an embodiment, the catalyst composition includes an activity limitingagent (ALA). As used herein, an “activity limiting agent” (“ALA”) is amaterial that reduces catalyst activity at elevated temperature (i.e.,temperature greater than about 85° C.). An ALA inhibits or otherwiseprevents polymerization reactor upset and ensures continuity of thepolymerization process. Typically, the activity of Ziegler-Nattacatalysts increases as the reactor temperature rises. Ziegler-Nattacatalysts also typically maintain high activity near the melting pointtemperature of the polymer produced. The heat generated by theexothermic polymerization reaction may cause polymer particles to formagglomerates and may ultimately lead to disruption of continuity for thepolymer production process. The ALA reduces catalyst activity atelevated temperature, thereby preventing reactor upset, reducing (orpreventing) particle agglomeration, and ensuring continuity of thepolymerization process.

The activity limiting agent may be a carboxylic acid ester, a diether, adiol ester, and combinations thereof. The carboxylic acid ester can bean aliphatic or aromatic, mono- or poly-carboxylic acid ester.Nonlimiting examples of suitable polycarboxylic acid esters includedimethyl phthalate, diethyl phthalate, di-n-propyl phthalate,diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate,di-tert-butyl phthalate, diisoamyl phthalate, di-tert-amyl phthalate,dineopentyl phthalate, di-2-ethylhexyl phthalate, and di-2-ethyldecylphthalate.

The aliphatic carboxylic acid ester may be a C₄-C₃₀ aliphatic acidester, may be a mono- or a poly- (two or more) ester, may be straightchain or branched, may be saturated or unsaturated, and any combinationthereof. The C₄-C₃₀ aliphatic acid ester may also be substituted withone or more Group 14, 15 or 16 heteroatom containing substituents.Nonlimiting examples of suitable C₄-C₃₀ aliphatic acid esters includeC₁₋₂₀ alkyl esters of aliphatic C₄₋₃₀ monocarboxylic acids, C₁₋₂₀ alkylesters of aliphatic C₈₋₂₀ monocarboxylic acids, C₁₋₄ alkyl mono- anddiesters of aliphatic C₄₋₂₀ monocarboxylic acids and dicarboxylic acids,C₁₋₄ alkyl esters of aliphatic C₈₋₂₀ monocarboxylic acids anddicarboxylic acids, and C₄₋₂₀ mono- or polycarboxylate derivatives ofC₂₋₁₀₀ (poly)glycols or C₂₋₁₀₀ (poly)glycol ethers. In a furtherembodiment, the C₄-C₃₀ aliphatic acid ester may be isopropyl myristate,di-n-butyl sebacate, (poly)(alkylene glycol) mono- or diacetates,(poly)(alkylene glycol) mono- or di-myristates, (poly)(alkylene glycol)mono- or di-laurates, (poly)(alkylene glycol) mono- or di-oleates,glyceryl tri(acetate), glyceryl tri-ester of C₂₋₄₀ aliphatic carboxylicacids, and mixtures thereof. In a further embodiment, the C₄-C₃₀aliphatic ester is isopropyl myristate or di-n-butyl sebacate.

In an embodiment, the activity limiting agent includes a diether. Thediether can be any di-ether represented by the structure (IV) aspreviously disclosed.

In an embodiment, the activity limiting agent includes a succinatecomposition having the following structure (VII):

wherein R and R may be the same or different, R and/or R′ including oneor more of the following groups: linear or branched alkyl, alkenyl,cycloalkyl, aryl, arylalkyl or alkylaryl group, optionally containingheteroatoms. One or more ring structures can be formed via one or both2- and 3-position carbon atom.

In an embodiment, the activity limiting agent includes a diol ester asrepresented by the following structure (VIII):

wherein n is an integer from 1 to 5. R₁ and R₂, may be the same ordifferent, and each may be selected from hydrogen, methyl, ethyl,n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, allyl, phenyl, orhalophenyl group. R₃, R₄, R₅, R₆, R₇, and R₈, may be the same ordifferent, and each may be selected from hydrogen, halogen, substituted,or unsubstituted hydrocarbyl having 1 to 20 carbon atoms. R₁-R₆ groupsmay optionally contain one or more heteroatoms replacing carbon,hydrogen or both, the hetero-atom selected from nitrogen, oxygen,sulfur, silicon, phosphorus and a halogen. R₇ and R₈, may be the same ordifferent, and may be bonded to any carbon atom of the 2-, 3-, 4-, 5-,and 6-position of either phenyl ring.

In an embodiment, the external electron donor and the activity limitingagent can be added into the polymerization reactor separately. Inanother embodiment, the external electron donor and the activitylimiting agent can be mixed together in advance and then added into thepolymerization reactor as a mixture. In the mixture, more than oneexternal electron donor or more than one activity limiting agent can beused.

In an embodiment, the catalyst composition includes any of the foregoingphosphites in combination with any of the foregoing alkoxysilanes and/orany of the foregoing activity limiting agents. Any of the presentcatalyst compositions may comprise two or more embodiments disclosedherein.

The present disclosure provides another catalyst composition. In anembodiment, a catalyst composition is provided which includes aprocatalyst composition, a cocatalyst, and an external electron donor.The procatalyst includes a magnesium moiety. The procatalyst compositionand the cocatalyst may be any respective procatalyst composition andcocatalyst as disclosed herein. The external electron donor comprises aphosphonite. The procatalyst composition and the cocatalyst may be anyrespective procatalyst composition and cocatalyst as disclosed herein.The catalyst composition may optionally include an alkoxysilane and/oran ALA. The alkoxysilane and/or the ALA may be any respectivealkoxysilane and/or ALA as disclosed herein.

In an embodiment, the phosphonite has the structure (IX):

wherein R₁ and R₂ are the same or different. Each of R₁ and R₂ isselected from a hydrocarbyl group having 1 to 20 carbon atoms, asubstituted hydrocarbyl group having 1 to 20 carbon atoms.

The term X represents a group selected from a hydrocarbyl group having 1to 20 carbon atoms, a substituted hydrocarbyl group having 1 to 20carbon atoms, a substituted amino group, an unsubstituted amino group, ahalide, a pseudohalide, or a hydroxyl group (—OH). As used herein, a“pseudohalide” refers to two or more atoms bounded together thatresemble a halide in charge and reactivity. Nonlimiting examples ofsuitable pseudohalides include azides, isocyanates, isocyanides,carboxylates, sulfonates, phosphinates, and phosphates.

As used herein, an “amino group” refers to a nitrogen-containingcompound derived from ammonia, a primary amine, or a secondary amine,with respective zero, one, or two, substituted (or unsubstituted)hydrocarbonyl groups having 1 to 20 carbons atoms. Nonlimiting examplesof suitable amino groups include —NH₂, —NHR₃, or —NR₃R₄, wherein R₃ andR₄ are substituted (or unsubstituted) hydrocarbonyl groups having 1 to20 carbons atoms. In an embodiment, R₃ and R₄ may be joined together orotherwise linked to form a ring structure. In a further embodiment, R₃and/or R₄ may be joined together or otherwise linked with R₁ and/or R₂of structure (IX) to form a ring structure. In an embodiment, X is asecondary amino group, and the structure (IX) is a phosphoramidite.

In an embodiment, X is a hydroxyl group (—OH). When X is a hydroxylgroup, the structure (IX) is a tautomer. A “tautomer,” as used herein,is a compound that is in chemical equilibrium between twointerconvertible structures resulting from the migration of a hydrogenatom. Thus, when X is a hydroxyl group, structure (IX) is a tautomer asdepicted by the equilibrium (X) below:

In an embodiment, any of R₁, R₂ and X, or at least two of R₁, R₂ and X,may be joined or otherwise linked together to form a P-ring structure.In an embodiment, the P-ring structure includes from 5 to 8 members. Inan further embodiment, each of R₁, R₂ and X are members of a P-ringstructure.

Nonlimiting examples of suitable P-ring structures for structure (IX)are set forth in Table B below.

TABLE B Structure Name

2-methyl-1,3,2-dioxaphospholane

N,N-dimethyl-1,3,2-dioxaphospholan-2-amine

2-ethoxy-1,2-oxaphosphinane

2-ethoxy-3-methyl-1,3,2-oxazaphospholidine

In an embodiment, R₁ and R₂ of structure (IX) are the same or different.X is a hydrocarbyl group. Each of R₁, R₂, and X is selected from a C₁-C₆alkyl group, and combinations thereof.

In an embodiment, R₁ and R₂ of structure (IX) are the same or different.X is a hydrocarbyl group. Each of R₁, R₂, and X is selected from amethyl group, an ethyl group, a propyl group, an isopropyl group, abutyl group, an isobutyl group, a C₅ ring structure, a C₆ ringstructure, and combinations thereof.

In an embodiment, each of R₁ and R₂ of structure (IX) is a methyl group.X is selected from a halide or a hydrocarbyl group. The hydrocarbylgroup is a C₁-C₆ alkyl group. The C₁-C₆ alkyl group is selected from amethyl group, an ethyl group, a propyl group, an isopropyl group, abutyl group, an isobutyl group, a C₅ ring structure, a C₆ ringstructure. In another embodiment, X is chloride.

In an embodiment, each of R₁ and R₂ of structure (IX) is an ethyl group.X is selected from a halide or a hydrocarbyl group. The hydrocarbylgroup is a C₁-C₆ alkyl group. The C₁-C₆ alkyl group is selected from amethyl group, an ethyl group, a propyl group, an isopropyl group, abutyl group, an isobutyl group, a C₅ ring structure, a C₆ ringstructure. In a further embodiment, X is chloride.

In an embodiment, each of R₁ and R₂ of structure (IX) is an ethyl group.X is a hydrocarbyl group that is a methyl group.

In an embodiment, the external electron donor may be complexed in wholeor in part with the cocatalyst.

In an embodiment, the external electron donor includes a phosphonite andan alkoxysilane. The alkoxysilane may be any alkoxysilane as disclosedherein. In a further embodiment, the external electron donor may includefrom about 0.1 mol % to about 99.9% mol % phosphonite and from about99.9 mol % to about 0.1 mol % alkoxysilane. In a further embodiment, thecatalyst composition includes an ALA.

In an embodiment, the external electron donor includes a phosphite and aphosphonite. The phosphite may be any phosphite as disclosed herein. Thephosphonite may be any phosphonite as disclosed herein. The externalelectron donor may contain from about 0.1 mol % to about 99.9 mol % ofthe phosphite and from about 99.9 mol % to about 0.1 mol % of thephosphonite. In an further embodiment, the external donor includes aphosphite, a phosphonite, and an alkoxysilane. In yet a furtherembodiment, the catalyst composition includes and ALA.

The present disclosure provides another catalyst composition. In anembodiment, a catalyst composition is provided which includes aprocatalyst composition, a cocatalyst, and an external electron donor.The procatalyst composition includes a magnesium moiety. The externalelectron donor comprises a pyrophosphite. The external electron donormay optionally include an alkoxysilane as discussed herein. The catalystcomposition may optionally include an activity limiting agent aspreviously disclosed herein.

The procatalyst composition may be any procatalyst composition asdisclosed herein. The cocatalyst may be any cocatalyst as disclosedherein.

The catalyst composition includes an external electron donor thatcomprises a pyrophosphite. The pyrophosphite has the structure (XI):

wherein R₁, R₂, R₃ and R₄ are the same or different and each is selectedfrom a substituted hydrocarbyl group having 1 to 20 carbon atoms, anunsubstituted hydrocarbyl group having 1 to 20 carbon atoms, andcombinations thereof.

In an embodiment, R₁-R₄ are the same or different. Each of R₁-R₄ ofstructure (XI) is selected from a C₁-C₆ alkyl group, and combinationsthereof.

In an embodiment, R₁-R₄ of structure (XI) are the same or different.Each of R₁-R₄ is selected from a methyl group, an ethyl group, a propylgroup, an isopropyl group, a butyl group, an isobutyl group, a C₅ ringstructure, a C₆ ring structure, and combinations thereof.

In an embodiment, each of R₁-R₄ of structure (XI) is a methyl group.

In an embodiment, each of R₁-R₄ of structure (XI) is an ethyl group.

In an embodiment, each of R₁-R₄ of structure (XI) is a butyl group.

In an embodiment, at least one R group, or at least two R groups ofR₁-R₄ are members of a P-ring structure. In an embodiment, the P-ringstructure includes from 5 to 8 members. In an further embodiment, eachof R₁-R₄ are members of a P-ring structure.

Nonlimiting examples of suitable P-ring structures for structure (XI)are set forth in Table C below.

TABLE C Structure Name

1,3,2-dioxaphospholan-2-yl diethyl phosphite

2,2′-oxybis(1,3,2-dioxaphospholane)

2,2′-oxybis(1,3,2-dioxaphosphinane)

In an embodiment, the external electron donor includes a pyrophosphiteand an alkoxysilane. The alkoxysilane may be any alkoxysilane asdisclosed herein. In a further embodiment, the external electron donormay include from about 0.1 mol % to about 99.9% mol % pyrophosphite andfrom about 99.9 mol % to about 0.1 mol % alkoxysilane.

In an embodiment, the external electron donor includes the pyrophosphitein combination with a phosphite and/or a phosphonite. The phosphite maybe any phosphite disclosed herein. The phosphonite may be anyphosphonite as disclosed herein. The external electron donor may containfrom about 0.1 mol % to about 99.9 mol % of the phosphonite, from about0.1 mol % to about 99.9 mol % of the phosphonite, and from about 99.9mol % to about 0.1 mol % of the pyrophosphite. In an further embodiment,the external donor includes a pyrophosphite, a phosphite and/or aphosphonite, and an alkoxysilane. In another embodiment, the catalystcomposition includes an ALA.

The present disclosure provides another catalyst composition. In anembodiment, a catalyst composition is provided which includes aprocatalyst composition, a cocatalyst, and an external electron donor.The external electron donor comprises a diphosphazane. The externalelectron donor may optionally include an alkoxysilane and/or an ALA asdisclosed herein.

The procatalyst composition may be any procatalyst composition disclosedherein. The cocatalyst may be any cocatalyst disclosed herein. In anembodiment, the procatalyst composition includes a magnesium moiety.

The catalyst composition includes an external electron donor thatcomprises a diphosphazane. The diphosphazane has the structure (XII):

wherein R₁, R₂, R₃ R₄ and R₅ are the same or different. Each of R₁-R₅ isselected from a substituted hydrocarbyl group having 1 to 20 carbonatoms, an unsubstituted hydrocarbyl group having 1 to 20 carbon atoms,and combinations thereof.

In an embodiment, R₁-R₅ are the same or different. Each of R₁-R₅ ofstructure (XII) is selected from a C₁-C₆ alkyl group, and combinationsthereof. In a further embodiment, each of R₁-R₅ is selected from amethyl group, an ethyl group, a propyl group, an isopropyl group, abutyl group, an isobutyl group, a C₅ ring structure, a C₆ ringstructure, and combinations thereof.

In an embodiment, each of R₁-R₄ of structure (XII) is an ethyl group. R₅is selected from a methyl group, an ethyl group, a propyl group, anisopropyl group, a butyl group, an isobutyl group, a C₅ ring structure,and a C₆ ring structure.

In an embodiment, each of R₁-R₄ of structure (XII) is an ethyl group andR₅ of structure (XII) is an isopropyl group.

In an embodiment, at least one R group of R₁-R₅ is a member of a P-ringstructure. In one embodiment, the P-ring structure includes a P—Olinkage and a P—N linkage. In another embodiment, the P-ring structureincludes from 5 to 8 members.

In an embodiment, at least two R groups of R₁-R₅ are members of one ormore P-ring structures. Any two R groups of R₁-R₅ may be members of thesame P-ring structure. Any two R groups of R₁-R₅ may be members of twodistinct P-ring structures. In an embodiment, each of R₁-R₅ is a memberof a P-ring structure.

Nonlimiting examples of suitable P-ring structures for structure (XII)are set forth in Table D below.

TABLE D Structure Name

Diethyl 1,3,2-dioxaphospholan-2- yl(methyl)phosphoramidite

Diethyl 2-ethoxy-1,3,2-oxaza- phosphinan-3-ylphosphonite

3-(1,3,2-dioxaphospholan-2-yl)-2- ethoxy-1,3,2-oxazaphosphinane

N-(1,3,2-dioxaphospholan-2-yl)-N- methyl-1,3,2-dioxaphosphinan-2-amine

In an embodiment, the external electron donor includes a diphosphazaneand an alkoxysilane. The alkoxysilane may be any alkoxysilane asdisclosed herein. In a further embodiment, the external electron donormay include from about 0.1 mol % to about 99.9% mol % diphosphazane andfrom about 99.9 mol % to about 0.1 mol % alkoxysilane. In anotherembodiment, the catalyst composition includes as ALA.

In an embodiment, the external electron donor includes diphosphazane incombination with a phosphite and/or a phosphonite, and/or apyrophosphonite. The phosphite, phosphonite, and pyrophosphonite may beany respective phosphite, phosphonite, or pyrophosphonite as disclosedherein. The external electron donor may contain from about 0.1 mol % toabout 99.9 mol % of the diphosphazene and from about 99.9 mol % to about0.1 mol % of the phosphite, and/or the phosphonite, and/or thepyrophosphonite. In an further embodiment, the external donor includesalkoxysilane. In another embodiment, the catalyst composition includesan ALA.

In an embodiment, a catalyst composition is provided which includes anexternal electron donor that includes a mixture of two or more of thefollowing: phosphite, phosphonite, pyrophosphite, and diphosphazane. Inone embodiment, the external electron donor is a mixture of any two(binary) of the foregoing compositions. In another embodiment, theexternal electron donor is a mixture of any three of the foregoingcompositions. In another embodiment, the external electron donor is amixture of all four of the foregoing compositions. In anotherembodiment, the catalyst composition containing any of the foregoingexternal electron donor mixtures may include an alkoxysilane and/or anALA.

In an embodiment, a process for producing an olefin-based polymer isprovided. The process includes contacting an olefin with a catalystcomposition under polymerization conditions. The catalyst compositionmay be any catalyst composition as disclosed herein. The process furtherincludes forming an olefin-based polymer.

In an embodiment, the catalyst composition includes an external electrondonor composed of one or more of the following: a phosphite, aphosphonite, a pyrophosphite, and/or a diphosphazane. The catalystcomposition may optionally include an alkoxysilane and/or an activitylimiting agent as previously disclosed.

As used herein, “polymerization conditions” are temperature and pressureparameters within a polymerization reactor suitable for promotingpolymerization between the catalyst composition and an olefin to formthe desired polymer. The polymerization process may be a gas phase, aslurry, or a bulk polymerization process, operating in one, or more thanone, reactor.

One or more olefin monomers can be introduced in a polymerizationreactor to react with the catalyst composition and to form anolefin-based polymer (or a fluidized bed of polymer particles).Nonlimiting examples of suitable olefin monomers include ethylene,propylene, C₄₋₂₀ α-olefins, such as 1-butene, 1-pentene, 1-hexene,4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene and thelike; C₄₋₂₀ diolefins, such as 1,3-butadiene, 1,3-pentadiene,norbornadiene, 5-ethylidene-2-norbornene (ENB) and dicyclopentadiene;C₈₋₄₀ vinyl aromatic compounds including styrene, o-, m-, andp-methylstyrene, divinylbenzene, vinylbiphenyl, vinylnapthalene; andhalogen-substituted C₈₋₄₀ vinyl aromatic compounds such as chlorostyreneand fluorostyrene.

In an embodiment, the olefin-based polymer can be a propylene-basedolefin, an ethylene-based olefin, and combinations thereof. In anembodiment, the olefin-based polymer is a propylene-based polymer.

In an embodiment, polymerization occurs by way of gas phasepolymerization. As used herein, “gas phase polymerization” is thepassage of an ascending fluidizing medium, the fluidizing mediumcontaining one or more monomers, in the presence of a catalyst through afluidized bed of polymer particles maintained in a fluidized state bythe fluidizing medium. “Fluidization,” “fluidized,” or “fluidizing” is agas-solid contacting process in which a bed of finely divided polymerparticles is lifted and agitated by a rising stream of gas. Fluidizationoccurs in a bed of particulates when an upward flow of fluid through theinterstices of the bed of particles attains a pressure differential andfrictional resistance increment exceeding particulate weight. Thus, a“fluidized bed” is a plurality of polymer particles suspended in afluidized state by a stream of a fluidizing medium. A “fluidizingmedium” is one or more olefin gases, optionally a carrier gas (such asH₂ or N₂) and optionally a liquid (such as a hydrocarbon) which ascendsthrough the gas-phase reactor.

A typical gas-phase polymerization reactor (or gas phase reactor)includes a vessel (i.e., the reactor), the fluidized bed, a distributionplate, inlet and outlet piping, a compressor, a cycle gas cooler or heatexchanger, and a product discharge system. The vessel includes areaction zone and a velocity reduction zone, each of which is locatedabove the distribution plate. The bed is located in the reaction zone.In an embodiment, the fluidizing medium includes propylene gas and atleast one other gas such as an olefin and/or a carrier gas such ashydrogen or nitrogen.

In an embodiment, the contacting occurs by way of feeding the catalystcomposition into the polymerization reactor and introducing the olefininto the polymerization reactor. In an embodiment, the process includescontacting the olefin with a cocatalyst. The cocatalyst can be mixedwith the procatalyst composition (pre-mix) prior to the introduction ofthe procatalyst composition into the polymerization reactor. In anotherembodiment, cocatalyst is added to the polymerization reactorindependently of the procatalyst composition. The independentintroduction of the cocatalyst into the polymerization reactor can occursimultaneously, or substantially simultaneously, with the procatalystcomposition feed.

In an embodiment, the process includes mixing the external electrondonor (and optionally the activity limiting agent) with the procatalystcomposition. The external electron donor can be complexed with thecocatalyst and mixed with the procatalyst composition (pre-mix) prior tocontact between the catalyst composition and the olefin. In anotherembodiment, the external electron donor and/or the activity limitingagent can be added independently to the polymerization reactor. In anembodiment, the procatalyst composition, the cocatalyst, and theexternal electron donor are mixed or otherwise combined prior toaddition to the polymerization reactor.

In an embodiment, a polypropylene homopolymer is produced in a firstreactor. The content of the first reactor is subsequently transferred toa second reactor into which ethylene (and optionally propylene) isintroduced. This results in production of a propylene-ethylene copolymerin the second reactor.

In an embodiment, a polypropylene homopolymer is formed via introductionof propylene and any of the present procatalyst compositions,cocatalysts, external electron donors, and activity limiting agents inthe first reactor. The polypropylene homopolymer is introduced into thesecond reactor along with ethylene (and optionally propylene) and anexternal electron donor and optionally an activity limiting agent. Theexternal electron donor and the activity limiting agent may be the sameas or different from the respective components used in the firstreactor. This produces a propylene-ethylene copolymer (i.e., an impactcopolymer) in the second reactor.

In an embodiment, the olefin is propylene. The process includes forminga propylene-based polymer having a melt flow rate (MFR) from about 0.01g/10 min to about 2000 g/10 min, or from about 0.01 g/10 min to about1000 g/10 min, or from about 0.1 g/10 min to about 500 g/10 min, or fromabout 0.5 g/10 min to about 150 g/10 min, or from about 1 g/10 min toabout 100 g/10 min. In a further embodiment, the propylene-based polymeris a polypropylene homopolymer.

In an embodiment, the olefin is propylene. The process includes forminga propylene-based polymer having a xylene solubles content from about0.5% to about 10%, or from about 1% to about 8%, or from about 1% toabout 5%. In a further embodiment, the propylene-based polymer is apolypropylene homopolymer.

In an embodiment, the olefin is propylene. The process includes forminga propylene-based polymer at production rate from about 5 kg/g/hr toabout 50 kg/g/hr, or from about 10 kg/g/hr to about 40 kg/g/hr. As usedherein “production rate” refers to the kilograms of polymer produced pergram of catalyst composition consumed in the polymerization reactor perhour.

The present polymerization process may comprise two or more embodimentsdisclosed herein.

The effectiveness of an external electron donor depends largely on itscompatibility with the procatalyst composition with which it is used.Not bounded by any particular theory, electrical and/or stericcompatibility between certain external electron donors and particularprocatalysts exists that yields better results than with the sameprocatalyst and less compatible external electron donors. Thiscompatibility is unpredictable as there are no outward suggestions thatone external electron donor will work better than another with aparticular procatalyst. As demonstrated by the present disclosure, thepresent catalyst compositions with an external electron donor comprisinga phosphite, and/or a phosphonite, and/or a pyrophosphite, and/or adiphosphazane demonstrate high stereoregularity, high activity, andimproved hydrogen response resulting in formant olefin-based polymers(propylene-based polymers in particular) with high isotacticity and highmelt flow.

DEFINITIONS

All references to the Periodic Table of the Elements herein shall referto the Periodic Table of the Elements, published and copyrighted by CRCPress, Inc., 2003. Also, any references to a Group or Groups shall be tothe Groups or Groups reflected in this Periodic Table of the Elementsusing the IUPAC system for numbering groups. Unless stated to thecontrary, implicit from the context, or customary in the art, all partsand percents are based on weight. For purposes of United States patentpractice, the contents of any patent, patent application, or publicationreferenced herein are hereby incorporated by reference in their entirety(or the equivalent US version thereof is so incorporated by reference),especially with respect to the disclosure of synthetic techniques,definitions (to the extent not inconsistent with any definitionsprovided herein) and general knowledge in the art.

The term “comprising,” and derivatives thereof, is not intended toexclude the presence of any additional component, step or procedure,whether or not the same is disclosed herein. In order to avoid anydoubt, all compositions claimed herein through use of the term“comprising” may include any additional additive, adjuvant, or compoundwhether polymeric or otherwise, unless stated to the contrary. Incontrast, the term, “consisting essentially of” excludes from the scopeof any succeeding recitation any other component, step or procedure,excepting those that are not essential to operability. The term“consisting of” excludes any component, step or procedure notspecifically delineated or listed. The term “or”, unless statedotherwise, refers to the listed members individually as well as in anycombination.

Any numerical range recited herein, includes all values from the lowervalue to the upper value, in increments of one unit, provided that thereis a separation of at least 2 units between any lower value and anyhigher value. As an example, if it is stated that the amount of acomponent, or a value of a compositional or a physical property, suchas, for example, amount of a blend component, softening temperature,melt index, etc., is between 1 and 100, it is intended that allindividual values, such as, 1, 2, 3, etc., and all subranges, such as, 1to 20, 55 to 70, 197 to 100, etc., are expressly enumerated in thisspecification. For values which are less than one, one unit isconsidered to be 0.0001, 0.001, 0.01 or 0.1, as appropriate. These areonly examples of what is specifically intended, and all possiblecombinations of numerical values between the lowest value and thehighest value enumerated, are to be considered to be expressly stated inthis application. In other words, any numerical range recited hereinincludes any value or subrange within the stated range. Numerical rangeshave been recited, as discussed herein, reference melt index, melt flowrate, and other properties.

The terms “blend” or “polymer blend,” as used herein, is a blend of twoor more polymers. Such a blend may or may not be miscible (not phaseseparated at molecular level). Such a blend may or may not be phaseseparated. Such a blend may or may not contain one or more domainconfigurations, as determined from transmission electron spectroscopy,light scattering, x-ray scattering, and other methods known in the art.

The term “composition,” as used herein, includes a mixture of materialswhich comprise the composition, as well as reaction products anddecomposition products formed from the materials of the composition.

The term “polymer” is a macromolecular compound prepared by polymerizingmonomers of the same or different type. “Polymer” includes homopolymers,copolymers, terpolymers, interpolymers, and so on. The term“interpolymer” means a polymer prepared by the polymerization of atleast two types of monomers or comonomers. It includes, but is notlimited to, copolymers (which usually refers to polymers prepared fromtwo different types of monomers or comonomers, terpolymers (whichusually refers to polymers prepared from three different types ofmonomers or comonomers), tetrapolymers (which usually refers to polymersprepared from four different types of monomers or comonomers), and thelike.

The term “interpolymer,” as used herein, refers to polymers prepared bythe polymerization of at least two different types of monomers. Thegeneric term interpolymer thus includes copolymers, usually employed torefer to polymers prepared from two different monomers, and polymersprepared from more than two different types of monomers.

The term “olefin-based polymer” is a polymer containing, in polymerizedform, a majority weight percent of an olefin, for example ethylene orpropylene, based on the total weight of the polymer. Nonlimitingexamples of olefin-based polymers include ethylene-based polymers andpropylene-based polymers.

The term, “ethylene-based polymer,” as used herein, refers to a polymerthat comprises a majority weight percent polymerized ethylene monomer(based on the total weight of polymerizable monomers), and optionallymay comprise at least one polymerized comonomer.

The term, “propylene-based polymer,” as used herein, refers to a polymerthat comprises a majority weight percent polymerized propylene monomer(based on the total amount of polymerizable monomers), and optionallymay comprise at least one polymerized comonomer.

The term “alkyl,” as used herein, refers to a branched or unbranched,saturated or unsaturated acyclic hydrocarbon radical. Nonlimitingexamples of suitable alkyl radicals include, for example, methyl, ethyl,n-propyl, i-propyl, 2-propenyl (or allyl), vinyl, n-butyl, t-butyl,i-butyl (or 2-methylpropyl), etc. The alkyls have 1 and 20 carbon atoms.

The term “substituted alkyl,” as used herein, refers to an alkyl as justdescribed in which one or more hydrogen atom bound to any carbon of thealkyl is replaced by another group such as a halogen, aryl, substitutedaryl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substitutedheterocycloalkyl, halogen, alkylhalo, hydroxy, amino, phosphido, alkoxy,amino, thio, nitro, and combinations thereof. Suitable substitutedalkyls include, for example, benzyl, trifluoromethyl and the like.

The term “aryl,” as used herein, refers to an aromatic substituent whichmay be a single aromatic ring or multiple aromatic rings which are fusedtogether, linked covalently, or linked to a common group such as amethylene or ethylene moiety. The aromatic ring(s) may include phenyl,naphthyl, anthracenyl, and biphenyl, among others. The aryls have 1 and20 carbon atoms.

The term “phosphonite” includes not only compounds with a phosphorusatom joined to two alkoxy groups plus a hydrocarbyl group, but alsocompounds and their tautomers in which the hydrocarbyl group is replacedwith a halogen (forming a halophosphonite) or an amino group (NR₂,forming a phosphoramidite), or a hydroxyl (—OH) group.

Test Methods

Melt flow rate (MFR) is measured in accordance with ASTM D 1238-01 testmethod at 230° with a 2.16 kg weight for propylene-based polymers.

Melt index for the ethylene-based polymers is measured in accordancewith ASTM D 1238-01 test method at 190° with a 2.16 kg weight forethylene-based polymers.

Xylene Solubles (XS) is measured using a NMR method as described in U.S.Pat. No. 5,539,309, the entire content of which is incorporated hereinby reference.

Xylene solubles may also be measured by flow-injection polymer analysis(FIPA) using a Viscotek GPCmax VE 2001 GPC solvent/sample module and TDA302 triple detector array. A detailed description of the FIPA method isdescribed in Journal of Applied Polymer Science, 2002, 85(10), 2178, andreferences therein.

Polydispersity Index (PDI) is measured by an AR-G2 rheometer which is astress control dynamic spectrometer manufactured by TA Instruments usinga method according to Zeichner G R, Patel P D (1981) “A comprehensiveStudy of Polypropylene Melt Rheology” Proc. of the 2^(nd) World Congressof Chemical Eng., Montreal, Canada. An ETC oven is used to control thetemperature at 180° C.±0.1° C. Plant nitrogen purged inside the oven tokeep sample from degradation by oxygen and moisture. A pair of 25 mm indiameter cone and plate sample holder is used. Samples are compressmolded into 50 mm×100 mm×2 mm plaque. Samples are cut into 19 mm squareand loaded on the center of the bottom plate. The geometries of uppercone is (1) Cone angle: 5:42:20 (deg:min:sec); (2) Diameter: 25 mm; (3)Truncation gap: 149 micron. The geometry of the bottom plate is 25 mmcylinder.

Testing Procedure:

-   -   The cone & plate sample holder are heated in the ETC oven at        180° C. for 2 hours. Then the gap is zeroed under blanket of        nitrogen gas.    -   Cone is raised to 2.5 mm and sample loaded unto the top of the        bottom plate.    -   Start timing for 2 minutes.    -   The upper cone is immediately lowered to slightly rest on top of        the sample by observing the normal force.    -   After two minutes the sample is squeezed down to 165 micron gap        by lower the upper cone.    -   The normal force is observed when the normal force down to <0.05        Newton the excess sample is removed from the edge of the cone        and plate sample holder by a spatula.    -   The upper cone is lowered again to the truncation gap which is        149 micron.    -   An Oscillatory Frequency Sweep test is performed under these        conditions:    -   i. Test delayed at 180° C. for 5 minutes.    -   ii. Frequencies: 628.3 r/s to 0.1 r/s.    -   iii. Data acquisition rate: 5 point/decade.    -   iv. Strain: 10%    -   When the test is completed the crossover modulus (Gc) is        detected by the Rheology Advantage Data Analysis program        furnished by TA Instruments.    -   PDI=100,000÷Gc (in Pa units).

By way of example and not by limitation, examples of the presentdisclosure will now be provided.

1. External Electron Donor

Table 1 below provides the compounds used as external electron donors.

TABLE 1 Abbre- Compound viation Structure Dicyclopentyl- dimethoxysilaneDCPDMS (D-donor)

n-Propyltrimethoxy- silane NPTMS (N-donor)

Diethyl methyl phosphite DEP-OMe

Triethyl phosphite TEP

Diethyl propyl phosphite DEP-OPr

Diethyl (9- (methoxymethyl)- 9H-fluoren-9- yl)methyl phosphite DEP-Flu

Diethyl methylphosphonite DEP-Me

Diethyl chloro- phosphite (diethyl chlorophosphonite) (diethylphosphoro- chloridite) DEP-Cl

Tetraethyl pyrophosphite (tetraethyl diphosphite) TEPP

Tetraethyl isopropyl diphosphazane (tetraethyl isopropylimino-diphosphite) TEID

2. Preparation of External Electron Donors.

Phosphites that are not commercially available are prepared fromphosphorous trichloride or diethyl chlorophosphite and the appropriatealcohol(s) according to the published methods: (a) Organic Syntheses,Coll. Vol. 4, p. 955 (1963); Vol. 31, p. 111 (1951) and/or (b) U.S.Patent Application Publication No. 2004/0106815. The alcohol(9-(methoxymethyl)-9H-fluoren-9-yl)methanol is prepared as described inU.S. Patent Application Publication Nos. 2004/0106814 and 2006/0142146.Diphosphazane compounds are prepared from diethyl chlorophosphite andthe appropriate primary amine by analogy to the published methods: (c)J. Chem Soc. 1964, 1543 and/or (d) Polyhedron 1993, 12(5), 533 and/or(e) Tetrahedron: Asymmetry 1995, 6(2) 427 and/or (f) J. Am. Chem. Soc.2004, 126, 14712 and/or (g) J. Organomet Chem. 2005, 690, 742.Alternatively, diphosphazanes can be prepared from a Cl₂PN(R)PCl₂(R=hydrocarbyl) intermediate and the appropriate alcohol(s) according topublished methods: (h) Inorg. Chem. 1982, 21, 2139 and/or (i) J.Organomet Chem. 1990, 390, 203 and/or (j) J. Organomet Chem. 2007, 692,1875.

3. Preparation of Catalyst Composition.

A slurry of SHAC™ 320 catalyst in mineral oil with 5.4 wt % solidscontent is prepared from a catalyst with a 2.68 wt % Ti content in thesolid component. A slurry of the catalyst composition is prepared bypremixing 0.20 g or 0.33 g of the 5.4% slurry (6.0 or 10.0 μmol Ti,respectively) with the appropriate molar amount of the external electrondonor, and 5.4 mL (1.5 mmol) triethylaluminum (as a 0.28 M solution) for20 minutes. The amount of external electron donor added is based on themolecular weight of the electron donor and ranges from 19-38 molarequivalents relative to Ti. All manipulations are performed in an inertatmosphere glovebox. After preparation, the catalyst slurry is loadedinto a polymerization reactor injector from a septa-capped vial using anintegrated needle, then injected into the reactor. Micromoles of Tiadded, the molar ratio of external donor to Ti, and the polymerizationresults are contained in Tables (2-5).

4. Polymerization.

Polymerizations are conducted in a stirred, 3.8 L stainless steelautoclave. Temperature control is maintained by heating or cooling anintegrated reactor jacket using circulated water. The top of the reactoris unbolted after each run so that the contents can be emptied afterventing the volatiles. All chemicals used for polymerization or catalystpreparation are run through purification columns to remove impurities.Propylene and solvents are passed through two columns, the first columncontaining alumina, the second column containing a purifying reactant(Q5™ available from Engelhard Corporation). Nitrogen and hydrogen gasesare passed through a single column containing Q5™ reactant.

After attaching the reactor head to the body, the reactor is purged withnitrogen while being heated to 140° C. and then while cooling toapproximately 30° C. The reactor is then filled with a solution ofdiethylaluminum chloride in isooctane (1 wt %) and agitated for 15minutes. This scavenging solution is then flushed to a recovery tank andthe reactor is filled with ˜1375 g of propylene. Hydrogen is added usinga mass flow meter and the reactor is brought to 62° C. The amount ofhydrogen added ranges from 1000-8000 SCC and is shown as H₂/C₃ molarratio in Tables (2-5). The catalyst is injected as a slurry in oil orlight hydrocarbon and the injector is flushed with isooctane three timesto ensure complete delivery. After injection, the reactor temperature isramped to 67° C. over 5 minutes, or maintained at 67° C. via cooling inthe case of large exotherms. After a run time of 1 hour, the reactor iscooled to ambient temperature, vented, the head is removed, and thecontents are emptied. Polymer weights are measured after dryingovernight or to constant weight in a ventilated fume hood.

Catalyst properties, process performance and resultant polymerproperties for catalysts containing the external electron donors ofTable 1 are provided in Tables (2-5).

TABLE 2 Phosphite and Diphosphazane Polymerizations (0.41 mol % H₂/C₃)External Eff XS by XS by μmol Electron EED:Ti Yield (kg/g FIPA NMR Meltflow Run # Ti Donor ratio PP (g) cat) (%) (%) (g/10 min) PDI 2-1a* 6.0DCPDMS 25 453 42.0 2.8 2.4 7.2 — 2-1b* 6.0 DCPDMS 25 347 32.2 2.9 2.74.6 4.78 2-1c* 6.0 DCPDMS 25 515 47.7 3.0 2.9 7.1 — 2-1d* 6.0 DCPDMS 25337 31.2 3.0 2.6 3.9 4.88 2-1e* 6.0 DCPDMS 25 487 45.1 2.8 2.7 8.2 —2-1f* 6.0 DCPDMS 25 368 34.1 2.5 2.8 8.9 5.14 2-1g* 6.0 DCPDMS 25 47844.3 2.6 2.5 7.6 — 2-1h* 6.0 DCPDMS 25 385 35.7 2.7 2.5 6.8 4.84 2-2 6.0DEP-OMe 19 374 34.7 4.5 — 261.3 hmf 2-3 6.0 DEP-OMe 25 402 37.3 4.2 —174.5 hmf 2-4 6.0 DEP-OMe 31 427 39.6 4.5 — 239.0 hmf 2-5 6.0 DEP-OMe 38335 31.0 4.1 — 240.3 hmf 2-6 6.0 TEP 19 289 26.8 4.0 — 235.9 hmf 2-7 6.0TEP 25 289 26.8 3.9 — 177.3 hmf 2-8 6.0 TEP 31 333 30.9 3.6 — 301.4 hmf2-9 6.0 TEP 38 314 29.1 3.6 — 301.4 hmf 2-10 6.0 DEP-OPr 19 331 30.7 4.4— 403.2 hmf 2-11 6.0 DEP-OPr 25 354 32.8 4.6 — 416.2 hmf 2-12 6.0DEP-OPr 31 319 29.6 4.6 — 417.2 hmf 2-13 6.0 DEP-OPr 38 319 29.6 4.0 —440.5 hmf 2-14 6.0 TEID 19 193 17.9 4.9 — 87.1 hmf 2-15 6.0 TEID 25 17115.8 4.6 — 81.5 4.51 2-16 6.0 TEID 31 182 16.9 4.7 — 92.1 hmf 2-17 6.0TEID 38 177 16.4 4.4 — 109.8 hmf *= comparative, not an example of thedisclosure EED = external electron donor PP = propylene-based polymerproduced (g) Eff = efficiency as determined by propylene-based polymerproduced (kg)/catalyst composition (g)/hr “—” = not determined hmf =“high melt flow” which renders a PDI measurement by rheology which mustbe extrapolated

TABLE 3 Phosphite, Pyrophosphite, and Diphosphazane Polymerizations(0.14 mol % H₂/C₃) XS External Eff by XS by Melt μmol Electron EED:TiYield (kg/g FIPA NMR flow Run # Ti Donor ratio PP (g) cat) (%) (%) (g/10min) PDI 3-1a* 10.0 NPTMS 25 365 20.7 — 2.1 3.6 3.88 3-1b* 10.0 NPTMS 25318 18.0 — 1.9 3.2 3.80 3-2 6.0 DEP-OMe 25 341 31.6 4.8 — 74.0 hmf 3-3a10.0 TEP 25 445 25.2 3.9 — 55.1 3.83 3-3b 6.0 TEP 25 296 27.4 4.4 — 62.1— 3-4 6.0 DEP-OPr 25 269 24.9 5.2 — 83.8 hmf 3-5 6.0 DEP-Flu 25 236 21.94.8 — 51.0 4.40 3-6a 10.0 TEPP 25 239 13.5 6.1 — 45.1 4.28 3-6b 10.0TEPP 25 249 14.1 6.0 — 29.1 4.39 3-7 6.0 TEID 25 127 11.8 4.9 — 26.44.96 *= comparative, not an example of the disclosure EED = externalelectron donor PP = propylene-based polymer produced (g) Eff =efficiency as determined by propylene-based polymer produced(kg)/catalyst composition (g)/hr “—” = not determined hmf = polymer is“high melt flow” and yields a PDI measurement by rheology which must beextrapolated

TABLE 4 Phosphite, Pyrophosphite, and Diphosphazane Polymerizations(1.09 mol % H₂/C₃) XS XS External Eff by by Melt μmol Electron EED:TiYield (kg/g FIPA NMR flow Run # Ti Donor ratio PP (g) cat) (%) (%) (g/10min) PDI 4-1a* 10.0 NPTMS 25 363 20.6 — 1.9 105.6 4.33 4-1b* 10.0 NPTMS25 370 21.0 — 1.7 87.1 4.37 4-2 6.0 DEP-OMe 25 395 36.6 4.9 — 824.9 hmf4-3a 10.0 TEP 25 697 39.5 3.8 — 890.4 hmf 4-3b 6.0 TEP 25 481 44.6 4.4 —905.5 hmf 4-4 6.0 DEP-OPr 25 375 34.8 4.1 — 1581.3 hmf 4-5 6.0 DEP-Flu25 232 21.5 4.6 — 705.6 hmf 4-6a 10.0 TEPP 25 198 11.2 5.9 — 612.6 hmf4-6b 10.0 TEPP 25 314 17.8 4.9 — 489.9 hmf 4-7 6.0 TEID 25 201 18.6 4.4— 253.6 hmf *= comparative, not an example of the disclosure EED =external electron donor PP = propylene-based polymer produced (g) Eff =efficiency as determined by propylene-based polymer produced(kg)/catalyst composition (g)/hr “—” = not determined hmf = polymer is“high melt flow” and yields a PDI measurement by rheology which must beextrapolated

TABLE 5 Phosphonite Polymerizations (1.09 mol % H₂/C₃) External Eff XSby XS by μmol Electron EED:Ti Yield (kg/g FIPA NMR Melt flow Run # TiDonor ratio PP (g) cat) (%) (%) (g/10 min) PDI 5-1a* 10.0 NPTMS 25 36320.6 — 1.9 105.6 4.33 5-1b* 10.0 NPTMS 25 370 21.0 — 1.7 87.1 4.37 5-26.0 DEP-Me 25 269 24.9 — 7.2 946.0 hmf 5-3 10.0 DEP-Cl 25 514 29.1 6.4 —726.6 hmf *= comparative, not an example of the disclosure EED =external electron donor PP = propylene-based polymer produced (g) Eff =efficiency as determined by propylene-based polymer produced(kg)/catalyst composition (g)/hr “—” = not determined hmf = “high meltflow” which renders a PDI measurement by rheology which must beextrapolated

It is specifically intended that the present disclosure not be limitedto the embodiments and illustrations contained herein, but includemodified forms of those embodiments including portions of theembodiments and combinations of elements of different embodiments ascome within the scope of the following claims.

1. A catalyst composition comprising: a procatalyst compositioncomprising a magnesium moiety; a cocatalyst; and an external electrondonor comprising at least one of a phosphite, phosphonite, pyrophosphiteand diphosphazane.
 2. The catalyst composition of claim 1 wherein theprocatalyst composition comprises a component selected from the groupconsisting of a titanium moiety, an internal electron donor, andcombinations thereof.
 3. The catalyst composition of claim 2 wherein theprocatalyst composition comprises an internal electron donor selectedfrom the group consisting of an aromatic acid ester, a diether, a silylester, and combinations thereof.
 4. The catalyst composition of claim 3wherein the phosphite has the structure (VI)

the phosphonite has the structure (IX)

the pyrophosphite has the structure (XI)

and the diphosphazane has the structure (XII)

wherein R₁, R₂, R₃, R₄ and R₅ are the same or different and each ofR₁-R₅ is selected from the group consisting of a substituted hydrocarbylgroup having 1 to 20 carbon atoms, an unsubstituted hydrocarbyl grouphaving 1 to 20 carbon atoms, and combinations thereof; and X is selectedfrom the group consisting of a hydrocarbyl group having 1 to 20 carbonatoms, a substituted hydrocarbyl group having 1 to 20 carbon atoms, asubstituted amino group, an unsubstituted amino group, a halide, apseudohalide, and a hydroxyl group.
 5. The catalyst composition of claim4 wherein the external donor is a phosphite and R₁-R₃ are the same ordifferent, and each of R₁-R₃ is selected from the group consisting of aC₁-C₆ alkyl group, and combinations thereof.
 6. The catalyst compositionof claim 5 wherein the external donor is a phosphonite and each of R₁,R₂, and X is the same or different, and each of R₁, R₂, and X isselected from the group consisting of a C₁-C₆ alkyl group, andcombinations thereof.
 7. The catalyst composition of claim 5 wherein theexternal donor is a pyrophosphite and R₁-R₄ are the same or differentand each of R₁-R₄ is selected from the group consisting of a C₁-C₆ alkylgroup, and combinations thereof.
 8. The catalyst composition of claim 5wherein the external donor is a diphosphazane and R₁-R₅ are the same ordifferent and each of R₁-R₅ is selected from the group consisting of amethyl group, an ethyl group, a propyl group, an isopropyl group, abutyl group, an isobutyl group, a C₅ ring structure, a C₆ ringstructure, and combinations thereof.
 9. The catalyst composition ofclaim 4 wherein the external electron donor comprises an alkoxysilane.10. The catalyst composition of claim 4 comprising an activity limitingagent.
 11. The catalyst composition claim 6 wherein each of R₁, R₂, andX is the same or different, and each of R₁, R₂, and X is selected fromthe group consisting of a methyl group, an ethyl group, a propyl group,an isopropyl group, a butyl group, an isobutyl group, a C₅ ringstructure, a C₆ ring structure, and combinations thereof.
 12. Thecatalyst composition of claim 6 wherein at least one of R₁, R₂, and X isa member of a P-ring structure.
 13. The catalyst composition of claim 7wherein R₁-R₄ are the same or different and each of R₁-R₄ is selectedfrom the group consisting of a methyl group, an ethyl group, a propylgroup, an isopropyl group, a butyl group, an isobutyl group, a C₅ ringstructure, a C₆ ring structure, and combinations thereof.
 14. Thecatalyst composition of claim 13 wherein at least one R group of R₁-R₄is a member of a P-ring structure.
 15. The catalyst composition of claim8 wherein at least one R group of R₁-R₅ is a member of a P-ringstructure.
 16. A polymerization process comprising: contacting, underpolymerization conditions, an olefin with a catalyst compositioncomprising an external electron donor comprising a member selected fromthe group consisting of a phosphite, a phosphonite, a pyrophosphite, adiphosphazene, and combinations thereof; and forming an olefin-basedpolymer.
 17. The process of claim 16 comprising a catalyst compositionof claim
 4. 18. The process of claim 17 wherein the olefin is propylene,the process comprising forming a propylene-based polymer having a meltflow rate from about 0.01 g/10 min to about 2000 g/10 min.
 19. Theprocess of claim 17 wherein the olefin is propylene, the processcomprising forming a propylene-based polymer having a xylene solublescontent from about 0.5% to about 10%.
 20. The process of claim 17wherein the olefin is propylene, the process comprising forming anpropylene-based polymer at production rate from about 10 kg/g/hr toabout 50 kg/g/hr.